Journal of Power Sources 100 (2001) 125148

Nickel-based rechargeable batteries

A.K. Shuklaa,*, S. Venugopalanb, B. Hariprakasha
a
Solid-state and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560012, India
b
Battery Division, Power Systems Group, ISRO Satellite Centre, Bangalore 560017, India

Abstract

Nickeliron (NiFe), nickelcadmium (NiCd), nickelhydrogen (NiH2), nickelmetal hydride (NiMH) and nickelzinc (NiZn)
batteries employ nickel oxide electrodes as the positive plates, and are hence, categorised as nickel-based batteries. This article highlights
the operating principles and advances made in these battery systems during the recent years. In particular, significant improvements have
been made in the NiMH batteries which are slowly capturing the market occupied by the ubiquitous NiCd batteries. # 2001 Elsevier
Science B.V. All rights reserved.

Keywords: Nickel-based rechargeable batteries; Sodiumnickel chloride batteries; Zebra batteries; Bode diagram

1. Introduction x 1 to b-NiOOH. The oxidation state of nickel is 2 in

b-Ni(OH)2 and 3 in b-NiOOH. On prolonged charging, b-
The chargedischarge reactions of the nickel electrode NiOOH transforms irreversibly to g-NiOOH, where the
have been expressed as [1] oxidation state of nickel is found to be 3.7, which corre-
discharge
sponds to a formula of H0.3NiO2. The mechanism of the
NiO2 2H2 O 2e @ NiOH2 2OH reaction shown by Eq. (2) involves an equivalent diffusion of
charge
hydrogen ions (protons) through the solid-state lattices of b-
0
E 0:49 V versus SHE (1) Ni(OH)2 and b-NiOOH such that there is a continuous
change in the composition of the active material between
In Eq. (1), NiO2 forms the active material of the positive
the fully-charged b-NiOOH and fully-discharged b-
plate with Ni(OH)2 as the discharged product which is
Ni(OH)2. Accordingly, Eq. (2) may as well be written as
reconstituted as NiO2 during recharge. In practice, b-
Ni(OH)2 is the discharged product and this is reconstituted discharge
b-NiOOH H e @ b-NiOH2 (4)
as b-NiOOH during recharge. Accordingly, Eq. (1) is better charge
expressed as
As shown in the Bode diagram (Fig. 1), g-NiOOH is
discharge
b-NiOOH H2 O e 
@ b-NiOH2 OH  electrochemically reversible with a-Ni(OH)2. Since a larger
charge number of electrons are exchanged per nickel atom during
E0 0:49 V versus SHE the a , g phase transition, a higher theoretical capacity is
expected for a nickel positive electrode comprising a-
The reversible electrode potential (Erev) for the nickel Ni(OH)2 than b-Ni(OH)2. However, in an alkaline medium,
positive electrode is expressed by the Nernst relationship as a-Ni(OH)2 transforms to b-Ni(OH)2 on ageing. Efforts [3]
  are therefore, being expended to synthesise alkali-stable a-
aNiOH2  aOH 
Erev 0:49  0:059 log (3) Ni(OH)2 which has a turbostatic layered-structure with an
aNiOOH aH2 O
interlayer spacing of ca. 8 A along its c-axis as against
In the light of the paper by Corrigan and Knight [2], it is interlayer spacing of only 4.6 A along the c-axis for the
appropriate to express b-Ni(OH)2 as H2NiO2 and b-NiOOH b-Ni(OH)2 (Fig. 2).
as HNiO2, both of which can be expressed by the general The low solubility-product (K sp 1035 ) of nickel
formula: HxNiO2, where x 2 refers to b-Ni(OH)2 and hydroxide provides excellent stability to it in an alkaline
medium. Although the solubility of Ni(OH)2 active material
*
Corresponding author. Tel.: 91-80-309-2795; fax: 91-80-360-1310. in concentrated potassium hydroxide solutions is signifi-
E-mail address: shukla@sscu.iisc.ernet.in (A.K. Shukla). cantly low, it cannot be ignored. In a recent publication,

0378-7753/01/$ see front matter # 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 8 - 7 7 5 3 ( 0 1 ) 0 0 8 9 0 - 4
126 A.K. Shukla et al. / Journal of Power Sources 100 (2001) 125148
Fig. 1. Bode diagram showing the transformations among various phases
of nickel positive electrode.
Thaller and Zimmerman [4] has shown that the charge
efficiency of the nickel electrode stored in the discharged
state can be considerably lower due to Ostwald ripening [5],
a process where thermodynamic stability is achieved by
reduction in the surface-area of crystallites of b-Ni(OH)2
through a dissolutionprecipitation process in which bigger
crystals grow at the expense of smaller crystals. This has
been experimentally verified by Borthomieu [6]. However,
the process is reversible and the material can be brought
back to its original crystal form through repeated charge
discharge cycling.
The nickel electrode involves homogeneous solid-state
oxidation of b-Ni(OH)2 to b-NiOOH during its charge and
vice versa during its discharge, with an inherently long
cycle-life. An ideally-reversible battery requires its electro-
des to be of the second kind, in which the active masses at its
electrodes form true solid solutions at all states-of-charge
values with the electrodes kept in contact with a common
electrolyte. There is a natural tendency for crystal growth
and consequent phase segregation with many of the battery
electrodes of the second kind. Hence, the formation and
preservation of homogeneous solid solutions of oxidants and
reductants or the prevention of phase segregation at the
electrodes may have to be realised using spacing agents
isomorphous with their active mass. The nickel oxide elec-
trode employs Co(OH)2 which is isomorphous both with b-
NiOOH and b-Ni(OH)2, as the spacing agent [7].
In the beginning, developmental work on large-scale
commercial applications of nickel electrodes was based
on pocket-plate technology initiated in Sweden, Germany
and US during 18971903. In pocket-plate technology, the
active material is first palletised with a conductive additive
Fig. 2. Layered-structures in (a) turbostratic a-Ni(OH)2 and (b) b-
Ni(OH)2.
and a binder, and the pellets are then wrapped in a perforated
nickel-plated steel sheet (pocket) to serve as a current
collector and also to provide mechanical support. The next
major improvement in nickel electrode structure was the
tubular-plate development by Edison in 1908 to restrict the
mechanical forces due to swelling of the positive active mass
and to extend the cycle-life of the electrodes during deep-
discharge cycling applications. In tubular-plate construc-
tion, perforated nickel-plated mild steel tubes were filled
with alternating layers of nickel hydroxide and nickel flakes/
graphite. The active material layers in the tube were com-
pacted as and when they were introduced into the tube. The
individual tubes had metal bands spaced at regular intervals
along the length of the tube in order to control active
material expansion during cycling. The tubes were then
crimped at the ends. A number of tubes were arranged in
parallel in a frame to form the tubular-plate electrode. Due to
the cumbersome manufacturing process and high production
cost, the tubular-plate nickel electrodes are no longer being
produced [8,9].
Sintered-plate technology is considered as an important
milestone in the development of nickel electrodes. The
development of sintered-nickel plaques was initiated by
Pflider in 1928 [8]. Sintering is defined as a thermal process
in which the loose nickel particles are transformed into a
coherent body at a temperature just below the melting point
of nickel in a reducing atmosphere. More than 50% of
batteries based on nickel electrodes being currently manu-
factured use sintered electrodes for the positive plate. In
sintered electrodes, a porous sintered plaque retains the
positive active material within the pores and serves to
conduct the electric current to and from the active material.
Sintered plaques are produced either by a wet-slurry process
or by a dry-powder (loose-powder) process. In both these
processes, sintered plaques are produced by locating a pure
nickel mesh or a perforated nickel-plated steel sheet cen-
trally across the thickness of the carbonyl nickel powder
(INCO 287) layer followed by sintering at temperatures
between 800 and 10008C in a reducing atmosphere. Wet-
slurry plaques are manufactured by coating on both sides of
a nickel-plated steel or nickel grid or other current collecting
material uniformly to a desired thickness with a viscous
slurry comprising carbonyl nickel powder (INCO 255), a
pore former/expander, binder and water, drying the plaques
to evaporate the water, and finally sintering them between
800 and 10008C in a reducing atmosphere. Sintered nickel
electrodes have been the dominant technology for several
decades in most applications. These consist of a porous
nickel plaque of sintered high surface-area nickel particles
impregnated with nickel hydroxide active material either by
chemical or electrochemical methods. The chemical impreg-
nation of the sintered nickel plaque involves filling the pores
with aqueous Ni(NO3)2, cathodically polarising the filled
plaque in NaOH solution to convert it to Ni(OH)2, rinsing,
drying and weighing. The weight pick-up is a measure of
capacity. The process is repeated until the weight pick-up
 A.K. Shukla et al. / Journal of Power Sources 100 (2001) 125148
meets the required capacity criteria. Electrochemical
impregnation of sintered nickel plaque involves cathodic
polarisation of the plaque in hot, aqueous or alcoholic
solution of Ni(NO3)2 of pH 3 at a current density between
5 and 75 mA cm2. The plaques may be passivated before
impregnation to avoid corrosion and material build-up on the
surface and eventual plate thickening, especially during the
aqueous impregnation process. The loose/dry-powder sin-
tering process is exclusively used in the production of
hermetically sealed aerospace NiCd and NiH2 cells.
The dry-powder process is labour intensive and hence,
expensive. The essential features of sintered plaques are
high-porosity, large surface-area and high electrical con-
ductivity in combination with good mechanical strength. For
commercial applications sintered-plates are produced by a
wet-slurry process. Sintered nickel electrodes have a rela-
tively higher inert to active material weight ratio, utilise an
excess amount of nickel per ampere hour, involve laborious
processing and require a number of effluent streams to avoid
environmental pollution. Hence, for large-scale applica-
tions, roll-compacted plastic-bonded electrodes are pre-
ferred for economical and cost-effective production of
nickel electrodes. In plastic-bonded electrodes, a plastic
binder is utilised to impart structural integrity to the elec-
trode. For such electrodes to function effectively, the binder
must provide sufficient structural integrity to the electrode
while maintaining particle to particle contact. Besides, the
electrolyte access to active material must not be restricted.
Sintered-nickel electrodes are fabricated either by press-
ing the active mass with a suitable binder and a conductive
additive on to a substrate of inert metal (pressed-plate
design) or by using sintered (inert) metal substrate to contain
the active mass in its pores. The presence of binder in the
pressed-plate design contributes to increased electrode resis-
tance. By contrast, the absence of binder reduces the struc-
tural integrity of the electrode. The conductive additive has
to form a continuous chain without which the electrode
resistance is further increased. In the sintered-plate design,
structural integrity is achieved without any binder in the
active mass and continuity of the conductive path is accom-
plished without any particulate additive to the active mass.
The sintered-plate configuration is inherently very efficient.
The degree of utilisation (Faradic efficiency) of nickel
positive electrodes varies from 60% for the pocket/
pressed-plate to 90% for the sintered-plate electrodes.
The superior performance of the latter is due to the property
of the sintered support which acts as a porous electrode as
well as a current collector. Introduction of new electrode
manufacturing techniques is likely to yield improvements in
future. The process of making sintered electrodes is a well
established art. Conventional sintered-electrodes normally
have a volumetric Coulombic capacity of about 500 Ah l1.
At present, in order to achieve higher loadings, foam and
pasted electrodes are being preferred.
Pasted nickel electrodes consist of nickel hydroxide par-
ticles in contact with a conductive network or substrate,
127
preferably having a high surface-area. There have been
several variants of these electrodes including the plastic-
bonded nickel electrodes which utilise graphite as a micro-
conductor, and the foammetal electrodes which utilise
high-porosity nickel foam as a substrate loaded with sphe-
rical nickel hydroxide particles and cobalt as conductivity-
enhancing additive. Indeed, pasted electrodes of the
foammetal type have penetrated the consumer market
due to their low cost and higher energy density in relation
to sintered nickel electrodes.
Foam nickel electrodes, which were introduced in the mid
1980s, function in a similar fashion to sintered-plate elec-
trodes. A major development at INCO laboratory has been
the invention of INCOFOAMTM, a high-porosity nickel
substrate [10]. The process involves production of the
high-purity nickel foam through single step process using
an INCO refinery intermediate gas stream. The excellent
throwing power of the gas decomposition results in a uni-
form nickel density distribution. This unique process allows
for the development of nickel foam of different thickness
and porosity to suit customer needs. A nickel frame work
with approximately 95% free volume is created by nickel
plating a porous synthetic material (polyurethane or acrylic
fibre) followed by pyrolysis of the plastic material. The
utilisation of active material in these electrodes is poorer
than in sintered-plates. The higher pore volume and larger
active material holding capacity (reduction in conducting
substrate weight) more than compensates for the loss of
utilisation efficiency and consequently improves the energy
density of the cell.
Fibre nickel electrodes were introduced into the market in
late 1970s. These electrodes are manufactured by nickel
plating a mat of synthetic fibres (graphite or plastic) by an
electroless method followed by sintering under compression
at 8008C in a hydrogen atmosphere to form mats with 90%
free volume and subsequent impregnation with the active
mass. Mechanical impregnation is used in all these advanced
technology electrodes which allows production of electrodes
with a thickness ranging from 0.6 to 10 mm without much
variation in the ratio of current conducting substrate to active
mass [8].
Nickel oxide electrodes constitute the positive plates of
various storage batteries, namely nickeliron (NiFe),
nickelcadmium (NiCd), nickelhydrogen (NiH2),
nickelmetal hydride (NiMH) and nickelzinc (NiZn)
rechargeable batteries. In the following sections, we will
discuss the electrochemistry and operating principles of
these nickel-based battery systems.
2. Nickeliron batteries
The NiFe battery was developed by Edison in the USA
and Jungner in Sweden in 1901. The battery is based on the
use of nickel oxyhydroxide (NiOOH) at the positive elec-
trode and iron at the negative electrode.
128 A.K. Shukla et al. / Journal of Power Sources 100 (2001) 125148
The chargedischarge reactions of the battery are
discharge
2NiOOH Fe 2H2 O @ 2NiOH2 FeOH2
charge
Ecell 1:37 V
Under deep-discharge, a NiFe cell with a negative-limited
configuration will undergo a further discharge reaction at a
potential that is lower than the first step represented by
reaction (5), i.e.
discharge
NiOOH FeOH2 @ NiOH2 FeOOH
charge
Ecell 1:05 V
The cell reactions are highly reversible in the alkaline
electrolyte, particularly, if the discharge is limited to the
first step. The reversibility at the two electrodes confers a
long chargedischarge cycle-life of the battery. The two sets
of electrodes are arranged alternately and interlaced with
porous separators usually of polyvinyl chloride, polyethy-
lene, polyamide or polypropylene. The whole electrode
stack is kept immersed in a solution of alkaline electrolyte
(30 wt.% aqueous KOH). Cell terminals and links are
usually made from nickel-plated mild steel. The cells are
provided with vents, which may be of different designs, to
prevent spillage and carbonation while permitting the escape
of gases produced in the cell. Positive-limited NiFe cells
yield better cycle-life [11]. Even under abusive usage that
involves mechanical shocks and vibrations, overcharge/
overdischarge and storage in a charged or discharged state,
the cycle-life of the NiFe battery, with deep-discharge
between cycles, is of the order of 3000 cycles and the
calendar life is about 20 years [1218].
The chargedischarge reactions at the negative electrode
of the NiFe cell occur in two steps [13,15,16,19,20]
represented as
discharge
Fe 2OH @ FeOH2 2e
charge
0
E 0:88 V versus SHE
and
discharge
FeOH2 OH @ FeOOH H2 O e
charge
0
E 0:56 V versus SHE
The mechanism of electrode reaction (7) involves both solid
and liquid phases (heterogeneous mechanism) with HFeO2
as the dissolved ion intermediate [2022] which, on further
discharge, converts to Fe(OH)2. Thus, the actual course of
the electrode reaction (7) is
discharge
Fe 3OH @ HFeO2  H2 O 2e
charge
followed by
discharge
HFeO2  H2 O @ FeOH2 OH
charge
During prolonged discharge of the iron-electrode, there is a
continuous change in the composition of active Fe(OH)2 to
d-FeOOH and, akin to the nickel positive electrode, the
mechanism of the electrode reaction involves diffusion of
(5) protons between the solid lattices of Fe(OH)2 and d-FeOOH.
As the transformation of Fe(OH)2 to d-FeOOH is a bulk
feature, the mechanism involved during the second dis-
charge step is homogeneous in nature [23].
The open-circuit potential of the charged alkaline iron-
electrode is always more cathodic than the hydrogen elec-
trode reaction in the same solution [24]. Consequently, iron
is thermodynamically unstable and suffers corrosion
(6) through local cells with hydrogen evolution reaction
2H2 O 2e ! H2 2OH
E0 0:83 V versus SHE (11)
as the conjugate reaction.
Besides, the dissolved oxygen in an alkaline solution can
also lead to an oxygen reduction reaction
O2 2H2 O 4e ! 4OH
E0 0:41 V versus SHE (12)
as a conjugate reaction during the corrosion of the iron-
electrode.
Owing to these corrosion reactions, the alkaline iron-
electrodes undergo a self-discharge of about 12% of their
nominal capacity per day at 258C. Hydrogen evolution also
occurs concomitantly while charging the alkaline iron-elec-
trodes and brings about a decrease in the charge acceptance.
The degree of utilisation (or the Faradaic efficiency) of iron-
electrode, based on reaction (7), varies from about 30% for
electrodes of commercially pure iron to 60% for electrodes
that comprise high-purity iron.
A typical chargedischarge curve of a commercial NiFe
cell is shown in Fig. 3, while discharge curves at different
rates at 258C are given in Fig. 4. The data show that the
nominal (operating or discharge) voltage of NiFe cells
(7)
(8)
(9)
(10)
Fig. 3. Typical chargedischarge curves for a NiFe cell.
 A.K. Shukla et al. / Journal of Power Sources 100 (2001) 125148
Fig. 4. Typical discharge curves for a NiFe cell at various rates at 258C.
Numbers on curves are discharge rates with C as the nominal Ah capacity
of the cell.
could vary from about 1.23 V at the C/8 rate to 0.85 V at the
C rate. The open-circuit voltage, as well as the nominal
voltage at discharge rates between C/10 and C/100 is
1.3 V. The discharge curves are fairly flat with the change
in the cell voltage at the C/8 rate, i.e. 1.32 Vat 10% depth-of-
discharge to about 1.15 V at 90% depth-of-discharge. The
discharge capacity of the NiFe battery or cell is not only
dependent on its discharge rate, but also on the operational
temperature as shown in Fig. 5. This limits the application of
NiFe batteries for high discharge at low temperatures.
The self-discharge profile of a NiFe cell shown in Fig. 6
indicates that the rate of self-discharge could be as high as
810% of the nominal capacity per day at an operational
temperature of about 408C. Therefore, at high ambient
temperatures, the NiFe battery is useful only for applica-
tions where the duty schedule permits a recharge at least on
Fig. 5. Discharge capacity at high and low temperatures for a NiFe cell
vs. rate of discharge. The band spread shown is due to differences in size,
type and number of cells in the battery packs.
129
Fig. 6. Discharge capacity of a NiFe cell at end of different periods of
storage.
every alternate day or so, in order that a minimum of 80% of
the nominal capacity be available during discharge. At 208C
and below, the self-discharge rate of the NiFe cell is,
however, considerably less. At these operational tempera-
tures, the interval between recharges could be a month or
more in order that the battery may be able to deliver at least
80% of its nominal capacity at any point of time.
At operational temperatures <308C, the chargedischarge
cycle-life of NiFe batteries is of the order of 3000 cycles
under normal conditions of use in industrial traction vehicles
and railway-carriage service that involve deep-discharge
between cycles, moderate vibrations, and shocks with fairly
regular duty schedules. Under similar conditions of usage, a
calendar life of about 20 years has been realised for the Ni
Fe batteries. But at operational temperatures of about 458C,
the service life of the NiFe battery is nearly 1500 charge
discharge cycles with about 8 years of calendar life. The wet
shelf-life of NiFe batteries in the discharged state exceeds 2
years. The battery provides the normal chargedischarge
cycle-life even after a continuous period of wet storage in its
discharged state. The wet shelf-life can be extended to 10
years or more with a reconditioning cycle every 6 months or
so. Therefore, even with irregular duty schedules or periods
of neglect under field conditions, the actual service life of
NiFe batteries remains unaffected. The only routine main-
tenance operation for batteries in service is the addition of
water to make up for the losses during overcharge.
NiFe batteries are usually charged galavanostatically.
Charging is usually performed at the C/5 rate for 7 h and
could go up to C/3 for 4 h. The higher charging rates are
permissible provided the temperature of the electrolyte at the
end-of-discharge does not exceed 458C. Typical charging
curves for a NiFe cell at 258C are shown in Fig. 7. The
130 A.K. Shukla et al. / Journal of Power Sources 100 (2001) 125148
Fig. 7. Typical charging curves for a NiFe cell at 258C. Numbers on
curves are charging rates with C as the nominal capacity of the cell.
average voltage at the normal C/5 rate charging is between
1.6 and 1.65 V up to about 50% state-of-charge (SOC). The
charging voltage gradually rises to
1.85 V at the end of full and nickelic hydroxide (charged active material). Cadmium
charge.
The key problem in the development of NiFe batteries is
poisoning of the iron-electrode [25]. As explained above, the
iron-electrode undergoes self-discharge as a result of the
corrosion reaction. It has been demonstrated that a substan-
tial improvement in the overall performance of NiFe cells
is possible by electrocatalysis of the iron-electrode reaction
[26,27]. Although a complete suppression of hydrogen
evolution appears to be difficult, but if this hydrogen is
recombined with evolved oxygen using a hydrogenoxygen
recombinant catalyst [28], then it may be possible to achieve
sealed NiFe batteries. This would revive commercial
interest in NiFe batteries. Owing to these problems, the
Fig. 8. Operating principle of a sealed NiCd cell.
iron-electrode in NiFe batteries was replaced with cad-
mium leading to development of the NiCd system.
3. Nickelcadmium batteries
Both Jungner and Edison contributed significantly to the
development of the NiCd battery. Initial work on NiCd
batteries was limited to pocket-plate technology. Tubular-
plate batteries were introduced by Edison in 1908 to restrict
the mechanical deformations caused due to swelling of the
positive-active mass in pocket-plate batteries and to extend
the cycle-life of batteries in deep-discharge cycling applica-
tions. Swelling of the positive-active mass was contained by
Edison by replacing graphite with nickel flakes as the
conductive diluent. However, owing to the cumbersome
manufacturing process and high cost of production such
tubular-plate batteries are no longer being manufactured.
In a NiCd cell, the chargedischarge reactions at the
nickel positive electrode (cathode) proceed via homoge-
neous solid-state mechanism through proton transfer
between nickelous hydroxide (discharged active material)
hydroxide is the discharged active material at the negative
electrode (anode) of the NiCd cell. During charge, cad-
mium hydroxide at the negative electrode is converted to
metallic cadmium via a dissolved complex intermediate
product as described below.
CdOH2 OH ! CdOH3  (13)
  
CdOH3 2e ! Cd 3OH (14)
The overall reaction at the negative electrode is
discharge
Cd 2OH @ CdOH2 2e
charge
0
E 0:81V versus SHE (15)
 A.K. Shukla et al. / Journal of Power Sources 100 (2001) 125148 131

Accordingly, the overall cell reaction is

discharge
2NiOOH Cd 2H2 O @ 2NiOH2 CdOH2
charge

Ecell 1:30 V (16)

To ensure proper functioning of the sealed NiCd cell under

a variety of operating conditions, it is designed to be
positive-limited. This insures that only O2 evolution occurs
under normal operating conditions which diffuses to the
cadmium electrode and combines with active cadmium to
form Cd(OH)2 according to the reaction

Cd 12 O2 H2 O ! CdOH2
Cd(OH)2 is converted to active Cd according to reaction (15)
during the cell charge. The negative to positive plate capa-
city ratio usually varies between 1.5 and 2. The discharge
reserve is typically between 15 and 20% of positive capacity
and the charge reserve or overcharge protection is about 30%
of positive capacity. Under deep-discharge conditions, due
to inevitable differences in storage capacities of series
connected cells in the battery, H2 evolution may occur at
the positive electrode which is consumed at a very low rate at
the positive electrode. Hence, repeated occurrence of over-
discharge may cause internal pressure build-up leading to
cell burst. The operating principle of a sealed NiCd cell is
depicted in Fig. 8.
The performance of NiCd cells depends on several
factors such as cell type, cell construction, manufacturing
(17)
Fig. 9. Charge characteristics of a pocket-plate cell at C/5 rate.
process and operating temperature, chargedischarge rates,
previous history of the cell, length of open-circuit stand, age
of the cells, etc. The typical charge characteristics of a
pocket-plate cell at C/5 rate at room temperature are shown
in Fig. 9. Effect of temperature, rate, cell design and type on
the charge characteristics of NiCd cells are shown in
Fig. 10. The voltage, temperature and pressure variations
during charge of a sealed NiCd cell are shown in Fig. 11.
The effect of temperature and rate on the discharge char-
acteristics of the sealed NiCd cells are shown in Fig. 12.
The available capacity as a function of temperature and

Fig. 10. (a) Charge voltage profiles for different types of NiCd battery at C/10 rate; (b) effect of cell design differences on voltage profile of different NiCd
cell types; (c) charge curves for a typical sealed NiCd cell at various rates and temperatures, and (d) effect of charge temperature on voltage profile of NiCd
cells.
132 A.K. Shukla et al. / Journal of Power Sources 100 (2001) 125148
Fig. 11. Voltage, temperature and pressure curves for constant-current
charge of a sealed NiCd cell.
discharge rate is shown in Fig. 13. A typical voltage profile
on polarity reversal of the NiCd cell is shown in Fig. 14 and
the individual electrode characteristics are shown in Fig. 15.
The charge retention characteristics of the NiCd cell are
depicted in Fig. 16.
The open-circuit voltage of the NiCd cells is indepen-
dent of KOH concentration between 20 and 30%. In prac-
tice, little change occurs in the amount of water especially in
vented/flooded electrolyte NiCd cells. In hermetically
sealed starved electrolyte cells, formation of water during
charge at the positive electrodes causes dilution of electro-
lyte in the pores of the positive plate active material and in
the immediate vicinity of the electrode bringing about a
voltage drop or an overvoltage. During high-rate charge
discharge at low temperatures, dilution of electrolyte in
pores of one electrode leads to freezing while an increase
in electrolyte concentration at the opposite electrode results
in precipitation of solid in its pores.
Several authors [2931] have investigated the effect of
foreign cations on the performance characteristics of the
nickel active material and its electrical conductivity. For
instance, cadmium inhibits electrode swelling and formation
of g-NiOOH, facilitates good charge acceptance at elevated
Fig. 12. Effect of discharge rate and temperature on the typical sealed Ni
Cd cell capacity after charge at 208C.
Fig. 13. (a) Discharge curves for a typical 1.2 Ah sealed NiCd cell at
various discharge rates; (b) discharge curves for a typical sealed NiCd
cell at various temperatures at C/2 rate.
temperatures in addition to good stability during cycling and
increases the overvoltage for O2 evolution. Zinc inhibits
electrode swelling and formation of g-NiOOH and increases
the overvoltage for O2 evolution. Lithium eliminates the
poisoning effect of iron and increases the overvoltage for O2
evolution. Iron decreases the overpotential for O2 evolution,
and hence, the electrode capacity. Arsenic acts as the best
inhibitor for loss of charge. Cobalt increases the charge
efficiency at high-temperature, inhibits loss of charge under
open-circuit storage, prevents electrode swelling and for-
mation of g-NiOOH, minimises number of formation cycles,
eliminates the second plateau in plastic-bonded electrodes,
increases the overvoltage for O2 evolution, maximises the
Fig. 14. NiCd cell polarity reversal voltages.
 A.K. Shukla et al. / Journal of Power Sources 100 (2001) 125148
Fig. 15. Discharge characteristics at C/5 rate of positive and negative
plates in a pocket-plate NiCd cell.
oxidation of nickel and increases the reversibility of Ni(II)/
Ni(III) reaction and cycle-life stability.
Due to the dissolutionprecipitation mechanism at the
cadmium electrode, the active mass in the electrode con-
tinuously changes on a microscopic scale. Depending on the
chargedischarge conditions, the intermediate products
migrate within the electrode. The amount, size, form and
the location where Cd and Cd(OH)2 crystals grow in an
electrode have a significant effect on the electrochemical
behaviour of the battery. The cycle-life of the cell depends
on the temperature at which chargedischarge cycles are
carried out. Low chargedischarge currents and high-tem-
peratures lead to the formation of large crystals of negative
active material adversely affecting charge acceptance,
energy storage and the discharge capacity of the electrodes.
High chargedischarge rates, low operating and storage
temperatures, and storage in discharged condition minimise
the growth of metallic cadmium and cadmium hydroxide
elevating the electrochemical behaviour of the negative
electrode.
The temperature coefficients of cadmium and nickel
electrodes are 1.01 and 0.50 mV K1, respectively.
Fig. 16. Charge retention curves for a sealed NiCd cell at various
temperatures.
133
The temperature coefficient of the NiCd cell is
0.51 mV K1. The potential of the Cd electrode is invar-
iant with the state-of-charge (SOC), but the Ni electrode
potential changes continuously (about 100 mV between 20
and 80% SOC) with its SOC. The exchange current density
of the Cd electrode is 7  107 A cm2 of geometrical
surface-area. There are three different forms of Cd(OH)2,
namely a, b and g. Among these, b-Cd(OH)2 is the most
stable phase with one molecule per unit cell. The g-phase has
four molecules per unit cell and dominates at low tempera-
ture. It is more active than the b-phase and is more easily
charged. The a-phase is poorly crystalline and has the
brucite structure. It is the only phase that contains water.
It is unstable in KOH and converts to b-Cd(OH)2. Perfectly
crystalline stoichiometric b-Cd(OH)2 is electrochemically
inactive. Indium is added to the cadmium electrode to make
it more active. Choking (clogging of pores) causes mass-
transfer limitation whereby the inner part of the electrode
ceases to participate in the chargedischarge process.
Agglomeration is the gradual accumulation of metallic
cadmium into clusters which reduces the available sur-
face-area. When NiCd cells begin to exhibit capacity
fading, tests using reference electrodes frequently show
problems with the cadmium electrode. Anti-agglomerants
are added to limit the Cd metal grain growth which mini-
mises loss of capacity, but improves the operating voltage.
The anti-agglomerants work as expanders, favour formation
of a-Cd(OH)2, provide protective colloid action, get
attached to highly active sites, form complexing reaction
with Cd, reduce size of crystals formed, and enhance the
dissolutionprecipitation process. Some of the anti-agglom-
erants are carboxy-methyl cellulose, ethyl cellulose, cetyl-
trimethyl ammonium bromide, iron, nickel, hydroxy-ethyl
cellulose, sodium laural sulphate, sulphonated castor oil,
sunflower oil, carbon and polyvinyl alcohol.
The overpotential for H2 evolution on Cd is between 0.5
and 0.8 V. But Nickel has very low overvoltage for H2
evolution. From H2 evolution considerations, sintered-plate
electrodes are not as useful as pocket-plate or pasted/roll-
compacted electrodes which do not contain metallic
nickel. Vented NiCd cells that do not contain nickel at
the Cd electrode are likely to have very low water consump-
tion. H2 evolution in sealed NiCd cells should be elimi-
nated. H2 reduction can occur at the nickel oxide electrode,
but is a slow process. H2 can diffuse through plastic and
metallic materials which could also affect the SOC of the
cell.
The typical discharge curves at various stages of cycling
for a sealed NiCd cell are depicted in Fig. 17. The shape of
the discharge curve changes appreciably on cycling. The
discharge profile at the beginning of life is flat, but after
cycling appears to have a distinct slope due to possible
formation of different phases of nickel oxyhydroxide during
extensive cycling or continuous overcharge. The charged
and discharged forms of the positive active material exist in
multiple phases. During normal chargedischarge cycling of
134 A.K. Shukla et al. / Journal of Power Sources 100 (2001) 125148
Fig. 17. Typical discharge curves at various stages of cycling for a sealed
NiCd cell.
chemically prepared active material, b-Ni(OH)2 is converted
to b-NiOOH on charge and vice versa on discharge. On
prolonged charging or on overcharge, b-NiOOH is con-
verted to g-NiOOH.
During 19921993, SAFT introduced a new range of
ultra-low maintenance (ULM) NiCd batteries for aircrafts
to limit the penetration of the sealed lead-acid battery into
the aircraft market [32]. ULM batteries have (i) thermally
welded cells to ensure leak tightness, (ii) melanging of
electrodes which ensures matched electrical performance
characteristics for a batch of cells, (iii) seam welded plate
tabs and copper cell links and terminals which provide lower
resistance and minimise voltage drop, (iv) gas barrier mem-
brane which prevents significant recombination and material
migration, and (v) flooded gas barrier design that ensures the
batteries to survive conditions which would destroy starved
electrolyte sealed cells.
Fibre-structured nickelcadmium (FNC) cells were first
developed by Hoppeke in Germany. These cells are currently
produced in large-scale by Acme Electric (USA) under a
licence from Hoppeke. In FNC cells, two negative electrodes
are arranged back-to-back with a highly porous recombina-
tion fibre-nickel structure in between two positive plates.
The O2 produced at the positive electrode during charge
recombines rapidly at the recombination structure maintain-
ing partial vacuum in the cell as shown in Fig. 18. Pressure
does not build-up significantly even during C-rate over-
charge. Low-pressure operation permits light weight plastic
cell cases. The FNC cells utilise mechanically impregnated
fibre electrodes for both negative and positive plates in
addition to employing recombination plates in split negative
design. The FNC cells offer significant improvement in
energy density, life and cost over traditional sintered-plate
cells.
Standard NiCd cells, which have been the workhorse for
storing electrical energy in spacecraft since the beginning of
space exploration, use an aqueous chemical impregnation
process for the fabrication of electrodes. During the pre-
508C) temperature with high
paration of electrodes by the chemical impregnation process
Fig. 18. Oxygen recombination structure in fibre-structured NiCd cells.
in acidic nickel/cadmium nitrate solution, a porous sintered
nickel plaque is employed due to which the positive elec-
trodes expand/swell considerably on cycling. Also, the non-
woven nylon separator used in standard aerospace cells
hydrolyses and contributes to cell failure. In order to
improve the operational life of hermetically sealed NiCd
cells in spacecraft applications, super NiCd cells were
proposed by Hughes in the mid 1980s. In super NiCd
cells, the loading of positive and negative active materials
into the porous sintered nickel structure is carried out
electrochemically instead of by the vacuum impregnation
process for conventional cells. Inert polymer impregnated
zircar cloth, which is quite stable in the KOH electrolyte,
replaces the polyamide separator. These changes have been
found to be effective in extending the life of NiCd cells
both in low earth orbit (LEO) and geo-synchronous earth
orbit (GEO) satellites. One of the main problems of these
cells is the room temperature storage capacity loss in the
discharged open or shorted conditions.
The aerospace division of Acme Electric (USA) has also
introduced a sealed maintenance-free battery system based
on the common vessel mono block (CVM) concept. The
CVM concept can be adapted for virtually any type of
battery utilising aqueous electrolyte. The CVM battery
operates as a single sealed unit rather than individual sealed
cells allowing the maximum performance without mainte-
nance. The CVM battery comprises flooded cells and a
metal-hydrogen regulator cell to consume H2 and O2 gases
generated during charge, overcharge, discharge and storage.
The cells share a common gas space with the regulator cell
and there is constant gaseous flow among the cells regardless
of whether H2 or O2 or both of these gases are consumed at
the regulator cell kept at constant potential. Consequently,
heat generation occurs only in the regulator cell. A smart
charger monitors the battery pressure, current and the reg-
ulator cell current and temperature. The water balance
among cells is maintained by means of water vapour trans-
port in the common gas space. Since the heat generation
during charge is limited to the regulator cell, it permits
battery operation at high (
charge-efficiency. The regulator cell current, temperature
 A.K. Shukla et al. / Journal of Power Sources 100 (2001) 125148
and pressure are used to derive the SOC of the cells. The
CVM battery is unique in offering no maintenance, fast-
charge, excellent performance over a wide temperature
range, high reliability and long cycle-life.
NiCd cells suffer from a memory effect which is
described as an apparent reduction in discharge voltage
and capacity to a pre-determined cut-off voltage resulting
from highly repetitive shallow chargedischarge cycle with
very little overcharge. The memory effect is reflected as a
step in the discharge curve of a cell. This is mainly observed
in hermetically sealed aerospace NiCd cells and does not
occur normally during commercial use. But, in practice, the
memory effect cannot exist (a) if the cells are charged to
100% of their actual capacity, (b) if the cells are discharged
to variable depth in each cycle, and (c) if the cells are
discharged below 1 V. Poor battery performance caused by
simple correctable application problems often attributed to
the memory effect are (a) high cut-off voltage, as cut-off
voltage higher than 1.1 V per cell may drastically reduce the
delivered capacity, and (b) high ambient temperature opera-
tion as high-temperature reduces charge acceptance at the
normal C/10 rate. The discharge voltage is also lowered
slightly. Hence, the capacity to a given cut-off voltage is
lowered, creating the illusion of memory. NiCd cells also
have voltage depression due to continuous trickle charge.
Voltage depression is principally a phenomenon associated
with sintered electrodes. During extended period of over-
charge, changes in morphology and composition of the
sintered nickel oxide electrodes can create a resistance effect
which typically depresses the discharge voltage up to about
100 mV per cell. Such a depression in cell voltage is more
pronounced at high operating temperatures. The effect of
long-term overcharge at elevated temperature on the dis-
charge profile is shown in Fig. 19. The memory effect was
initially attributed to the Cd electrode and, even today, the
mechanism of this phenomenon is not fully understood. One
of the explanations has been that the unused portion of the
Fig. 19. Effect of long-term overcharge on the discharge capacity of Ni
Cd cells at elevated temperatures.
135
charged negative active material undergoes morphological
changes causing additional voltage drop during discharge.
Another opinion is that high-temperature overcharge favours
the formation of intermetallic alloys, such as Ni5Cd21, which
have a discharge potential more positive (ca. 150 mV) than
the Cd electrode. The amount of intermetallic phases
increases with the overcharge duration and the available
capacity gradually decreases in the high-voltage plateau.
Nickel hydroxide may be deliberately added or produced by
corrosion of the sintered nickel substrate during the impreg-
nation process. The solution to this problem is to eliminate
or minimise nickel hydroxide in the Cd electrode. The alloy
formation may be prevented by not using nickel as the
substrate or current collector material in the negative elec-
trode.
A freshly-charged positive electrode undergoes fairly fast
self-discharge due to instability of the higher oxidation state
of nickel (NiO2) formed towards the end-of-charge. Charged
positive active material is thermodynamically unstable and
can spontaneously decompose with evolution of O2 accord-
ing to the reaction
2NiOOH H2 O ! 2NiOH2 12 O2 (18)
After termination of charge, gas evolution continues with the
decomposition of the charged active material. The rates of
decomposition and recombination depend on the tempera-
ture, structure of the active material and several other factors
such as inter-electrode spacing, presence of gas diffusion
membranes such as cellophane. The highly facile O2 recom-
bination reaction at the Cd electrode can accelerate the
decomposition of positive active material according to
reaction (17).
The positive and negative electrodes may contain nitrate
ions which lead to nitrate (NO3)nitrite (NO2) shuttle
reactions due to the presence of impurities as described
below.
NO3  H2 O 2e ! NO2  2OH (19)
  
NO2 5H2 O 6e ! NH3 7OH (20)
NO3  H2 O Cd ! NO2  CdOH2 (21)
 
NO2 3Cd 5H2 O ! NH3 3CdOH2 OH (22)
NH3 7OH ! NO2  5H2 O 6e (23)
NH3 6NiOOH H2 O OH ! 6NiOH2 NO2 
(24)
NO2  2NiOOH H2 O ! 2NiOH2 NO3  (25)
The NO3NO2 shuttle reaction continues until the cell
is totally discharged or NH3 is deactivated by the reaction
2NH3 6NiOOH ! N2 6NiOH2 (26)
leaving a permanent N2 pressure within the cell. The capa-
city retention characteristics in NiCd cells improve as the
cell ages due to conversion of nitrate ions to N2 gas.
136 A.K. Shukla et al. / Journal of Power Sources 100 (2001) 125148
Oxidation of organic impurities that are extracted or
leached out from the separator at the positive electrode
cause self-discharge of the cells. It is suggested that the
main contributing factor is the decomposition of conven-
tional polyamide separator with the production of ammonia
and amines which participate in shuttle reactions similar to
NO3 ions [33]. The charge retention can be drastically
improved by using chemically stable separators such as
polymer impregnated zircar or sulfonated polypropylene.
It has been possible to decrease the self-discharge rate of Ni
Cd cells by incorporating certain inhibitors for the oxygen-
evolution reaction, such as CdO, with the active material.
NiCd cells exhibit higher than normal end-of-charge
voltage on constant current charge after open-circuit-stand
due to slow deactivation of the negative electrode. Perma-
nent build-up of internal pressure may occur due to H2
evolution if the charge voltage exceeds 1.5 V at room
temperature (258C). Besides, NiCd batteries have a fairly
high rate of self-discharge at high-temperatures. But worst
of all, cadmium is an awful poison that can contaminate the
environment. The unpopularity of cadmium has encouraged
the development of alternate nickel-based batteries, namely
NiH2 and NiMH batteries.
4. Nickelhydrogen batteries
In a NiH2 cell, the cadmium electrode of the NiCd cell
is replaced with a light weight hydrogen-gas electrode
which increases the gravimetric energy density of the cell
significantly, but its volumetric energy density happens to
be lower in relation to any other nickel-based battery. The
system was specifically developed for aerospace applica-
tions. Initial development of NiH2 cells was sponsored by
COMSAT Laboratory, US Air Force and Hughes Aircraft
Company for use in GEO and LEO satellites [34]. The
Fig. 20. Back-to-back stacking configuration in a NiH2 cell.
COMSAT design uses an asbestos separator, a Teflon
coating on the inner walls of the pressure vessel, and
Zeigler seals for the feed-through terminals with the elec-
trode leads running along the edges of the electrode stack.
Hughes design uses zirconium oxide separator, plasma
sprayed zirconium oxide coating on the inner walls of the
pressure vessel, Teflon compression feed-through term-
inals, and a pineapple slice electrode configuration with
electrode leads running through the centre of the stack
allowing very short distances between the electrode stack
and the pressure vessel wall [35]. There have been several
modifications and improvements in NiH2 batteries during
the past several years [34]. The State-of-the-art, NiH2 cell
uses a combination of these two designs with ceramic or
Zeigler feed-through terminals, single or two layers of
zirconium oxide separator and plasma sprayed zirconium
oxide coating on the inner walls of the pressure vessel [36].
Two types of electrode stacking configurations employed in
the NiH2 cells are (i) back-to-back stacking configuration
shown in Fig. 20, and (ii) the recirculating design stacking
in which the positive electrode, separator, negative elec-
trode and gas screens are stacked sequentially.
NiH2 cells have fewer inherent failure mechanisms than
NiCd cells and exhibit higher reliability and longer cycle-
life. The other life-limiting component, namely the nylon
separator, is replaced by zircar, a thin and porous zirconia
ceramic sheet which reduces the electrolyte redistribution
and improves the operational life of NiH2 cells consider-
ably in relation to NiCd cells.
The chargedischarge reactions at the nickel electrode of
a NiH2 cell are the same as in NiCd cell. The reaction at
the hydrogen electrode during normal operation is
discharge
1
2 H2 OH @ H2 O e
charge
0
E 0:83 V versus SHE (27)
 A.K. Shukla et al. / Journal of Power Sources 100 (2001) 125148 137

Accordingly, the net cell reaction is electrode can also cause dissolution of platinum at the
discharge
negative electrode according to the reaction
1
2 H2 NiOOH @ NiOH2 Ecell 1:32 V (28)
charge 2Pt O2 4OH 2H2 O ! 2PtOH4 2 (37)
During overcharge O2 is generated at the positive electrode Reactions at the hydrogen electrode during shorted sto-
which is electrochemically recombined at the catalytic rage of cells with nickel pre-charge are
platinum negative electrode. Since O2 recombination at
the negative platinum electrode is fast, the cell can sustain 4OH ! 2H2 O O2 4e (38)
continuous overcharge at very high rates provided the heat and
generated is effectively dissipated to avoid any thermal run-
away. 2Pt O2 4OH 2H2 O ! 2PtOH4 2 (39)
The parasitic reaction and reaction during overcharge at
the nickel electrode is The electrode reaction during storage in cells with hydro-
gen pre-charge is
4OH ! 2H2 O O2 4e (29)
3CoOOH 12 H2 ! Co3 O4 2H2 O (40)
The electrochemical reaction during overcharge of the
hydrogen electrode is Since cobalt is an essential component of these electrodes
  this results in permanent capacity loss of the NiH2 cells.
2H2 O O2 4e ! 4OH (30) NiH2 cells are mainly employed in spacecraft for on-
The chemical recombination reaction at the negative elec- board energy conversion and storage. Various configurations
trode is of NiH2 spacecraft batteries are (a) independent pressure
vessel (IPV) batteries, (b) common pressure vessel (CPV)
H2 12 O2 ! H2 O (31) batteries, (c) single pressure vessel (SPV) batteries, (d)
Depending on whether the capacity is limited by the nickel dependent pressure vessel (DPV) batteries, and (e) bipolar
oxide electrode or the hydrogen electrode, one can have batteries.
a positive-limited (hydrogen pre-charge) or negative-limited IPV batteries contain only one cell stack per pressure
(nickel pre-charge) cell. All NiH2 cells manufactured vessel. In common pressure vessel batteries, there are two or
till the mid-1980s were H2-pre-charge type. In a H2-pre- more cell stacks electrically connected in series. A two cell
charge cell, the reaction during reversal at the nickel elec- CPV design provides 50% reduction in cell mounting foot
trode is print with the number of cell units less than the IPV design.
There is a 30% reduction in battery volume and 15%
H2 O e ! OH 12 H2 (32) reduction in battery mass. In SPV design, the required
In a H2-pre-charge cell, during reversal the normal discharge number of cells forming the battery are electrically con-
reaction taking place at the H2 electrode is nected in series and placed in a single pressure vessel. This
design offers advantages of reduction in mass, volume and
1
2 H2 OH ! H2 O e (33) cost. The major disadvantage is that failure of any one cell
results in failure of the entire battery. The SPV batteries can
During reversal of a nickel pre-charged cell, the normal
be configured to deliver a wide range of capacities and
discharge reaction proceeding at the nickel electrode is
voltage outputs. The SPV batteries are less reliable than IPV
2NiOOH 2H2 O 2e ! 2NiOH2 2OH (34) and CPV cells. The DPV technology is a modular approach
to NiH2 space battery design [37].
In a nickel pre-charged cell, O2 evolution occurring at the H2 The basic NiH2 cells comprise a stack of electrodes with
electrode during reversal is alternating pairs of positive nickel and negative hydrogen
4OH ! 2H2 O O2 4e (35) electrodes separated from each other with a zircar separator
wetted with potassium hydroxide electrolyte solution so
The net reaction during reversal of a positive pre-charged as to provide electronic insulation and ionic conduction
cell is given as between the anode and the cathode, and all contained in a
2NiOOH H2 O ! 2NiOH2 12 O2 (36) cylindrical pressure vessel with hemispherical end caps
provided with hermetically sealed feed-through terminals
When a positive pre-charge cell is forced into reversal after for the electrodes. The pressure vessel of a NiH2 cell is
all the H2 is consumed, O2 is generated at the H2 electrode highly prone to single point failure. Therefore, identifica-
until the positive nickel oxide electrode is fully-discharged. tion of fracture critical flaws on the surface of the material
The generated O2 is consumed during recharge of the cell. or at a welded seam is important. The vessel must meet
During reversal of a nickel positive pre-charge cell, there is a the criteria established in MIL-STD 1522A for hermeti-
possibility for formation of an explosive mixture of H2 and city and strength. The pressure vessel design should have a
O2 in the cell. The O2 evolution reaction at the platinum burst strength three times the maximum expected operating
138 A.K. Shukla et al. / Journal of Power Sources 100 (2001) 125148
pressure. The terminal bosses are injection moulded with
Nylon bushing which, when crimp fitted to the cell terminal,
form the Ziegler compression seal to provide hermeticity. Its
exceptional strength precludes terminal rotation during nor-
mal handling, testing and battery assembly.
The cell stack in back-to-back configuration is assembled
on a moulded plastic (polysulfone) core which is channelled
to accommodate plate lead bundles. The polysulfone core
provides light weight, high strength and compatibility with
caustic electrolyte. The stack is confined between two
polysulfone end plate assemblies. Belleville spring washers
permit uniform stack compression and help accommodating
positive-plate growth.
The negative hydrogen electrode consists of a Teflon-
bonded platinum black catalyst supported on a fine mesh
nickel screen with a microporous gas-diffusion Teflon back-
ing film. The catalyst loading is about 58 mg cm2. The
microporous Teflon backing membrane avoids water/elec-
trolyte loss from the rear of the negative platinum electrode
during charge and overcharge while readily allowing diffu-
sion of hydrogen and oxygen gases. A photo-etched nickel
substrate eliminates cut edges of the electrodes that could
cause shorting during cell stack assembly and provides solid
tabs for lead attachment. Hydrogen electrode should provide
the right interface for the electrochemical reactions to occur
without flooding or drying out the electrodes at the separator
interface.
The positive plate consists of 35 mil (
1 mm) thick dry Accordingly, the cell weight is reduced.
sintered porous nickel plaques electrochemically impreg-
nated with nickel hydroxide active material to the extent of
1.65 g cm3 of void volume. A pure nickel wire mesh
substrate is centred in the electrode structure to provide
electrical and structural benefits. A bend strength of 900 psi
is ensured for the sintered nickel plaque at 84% porosity
level to provide long-term dimensional stability to the
electrodes. The plate typically delivers a capacity greater
than 125% of the theoretical value (calculated for one
electron transfer reaction) during flooded capacity checks
at the component level.
In older designs, non-woven asbestos was used as the
separator material which offers high bubble pressure and
prevents rapid recombination of H2 and O2 at the negative
electrode. A pressure differential of more than 25 psi is
required to force O2 bubbles through the separator. Asbestos
has dual pore size distribution which helps preventing
separator dryout. Currently, ZYK-15H untreated knit cloth
type zircar separator is exclusively used in all hermetically
sealed aerospace NiH2 cells. Zircar has very good stability
in the caustic electrolyte allowing long-term storage and/or
cycling. Cells with zircar separator have lower impedance
and better discharge voltage performance. Zircar has
low bubble pressure and allows permeation of O2 gas for
recombination at the negative electrode. Zircar tends
to retain the thickness under compression and holds
relatively more electrolyte per unit volume of the separator.
But, it is very fragile and must be handled with care.
A polypropylene gas spacer screen is used within the stack
for gas management.
At present, state-of-the-art NiH2 cells use nickel pre-
charge where the capacity of the cell is limited by the
negative active material on discharge. Some of the design
parameters such as bend strength of the positive sinter,
loading level of the positive electrode and the concentration
of the electrolyte strongly influence the cycle-life of NiH2
cells. Higher concentration of electrolyte stabilises higher
oxides of nickel and the electrode capacity increases with
electrolyte concentration between 21 and 38% aqueous
KOH in NiH2 cells. There is ample evidence that lower
concentration of electrolyte reduces corrosion of the sin-
tered-nickel substrate, as also the plate growth especially in
high-porosity sintered-plates, but at the cost of lower capa-
city. Generally, lower concentration of electrolyte (26%
aqueous KOH) is recommended for LEO satellites while
a higher concentration of electrolyte (31% aqueous KOH) is
used in GEO satellites. Cells without nickel pre-charge are
often found to develop low capacity and/or a second plateau
below 1 V level after a prolonged storage period. Nickel pre-
charge has been tested by numerous independent investiga-
tors in the industry with pronounced beneficial effects. The
principal benefit is the reduction of capacity decay on
storage. In addition, nickel pre-charge provides better
charge-retention, lower charge-voltage, a slightly higher
discharge voltage and lower operating pressure for the cell.
A catalysed wall wick serves as electrolyte concentrator
and inventory equilibrator and as a reservoir. The vessel wall
is coated with yttria-stabilised zirconia by a plasma spraying
technique to form a porous layer to serve as wall wick. Since
the H2O2 recombination reaction is highly exothermic, it is
desirable to locate the recombination sites close to the heat
removal mechanism. This is done by coating the wall wick
with platinum black to form strips of catalytic sites where
the H2O2 recombination reaction can occur. In cells, where
a passive cooling system is used, heat is removed from the
pressure vessel wall. The advantage of producing H2O2
recombination outside the stack and on the wall of the
pressure vessel is the ease of heat rejection. The catalysed
wall wick also allows the cell to run cooler.
Foam electrodes which were introduced in the mid 1980s
function akin to sintered-plate electrodes. A nickel frame
work with approximately 95% free volume is created by
nickel plating a porous synthetic material comprising poly-
urethane or acrylic fibre and subsequent pyrolysis of the
plastic material. The utilisation of active material in these
electrodes was poorer than in sintered-plates. The higher
pore volume and larger active material holding capacity
(reduction in conducting substrate weight) more than com-
pensates for the loss of utilisation efficiency and conse-
quently improves the energy density of the cell.
Independent pressure vessel (IPV) NiH2 batteries suffer
from inefficient grouping of multiple cylindrical cells in the
battery pack. DPV design offers a higher energy density and
 A.K. Shukla et al. / Journal of Power Sources 100 (2001) 125148
reduced cost with an efficient mechanical, electrical and
thermal cell configuration in addition to a reduced parts
count. A unique feature of the DPV cell design is the
prismatic electrode stack which provides an optimum geo-
metry for the pressure vessel. The flat sides of the pressure
vessel are supported by the end plates in the final battery
assembly. Dependent pressure vessel geometry requires the
cell to be externally supported to contain the hydrogen
pressure developed inside the cell during charging. Since
the pressure vessel is not required to sustain the full internal
pressure, it is made thinner to reduce the weight. The round
edge of the pressure vessel over a relatively small radius
efficiently supports the full internal pressure with minimum
weight of the pressure vessel material. The pressure vessel is
made of stainless steel and consists of two identical seamless
halves with a lip around the edge where the two halves meet
to assist in laser welding for hermetically sealing the cell.
One of the pressure vessel halves is fitted with cell terminal
bosses and a fill tube. The cell terminal uses an internal boss
arrangement which has minimum external protrusion and
minimises overall dimensions of the cell.
The electrode stack consists of nickel oxide and hydrogen
electrodes interspersed with absorbent polymeric separator
material. A back-to-back arrangement with each nickel
electrode facing the catalyst side of the hydrogen electrode
is employed. In this arrangement, the hydrophobic sides of
the hydrogen electrodes face each other. A gas spacer is
inserted in order to facilitate gas diffusion towards and away
from the hydrogen electrode during charge and discharge
reactions.
A metal stacking bracket spot welded to one half of the
pressure vessel holds the electrode stack in place within the
cell pressure vessel. The stack is kept electrically isolated
from the stacking bracket and the pressure vessel. The
electrical tabs emerge through a window in the stacking
bracket. The positive and negative lead bundles from the
stack are given stress relief loops before attachment to
terminal posts to prevent any mechanical stress owing to
launch vibrations being transmitted to the electrode/tab
connection. The cells are connected in series to form the
battery assembly. In a DPV battery assembly, the cells are
sandwiched between two end plates which is a standard
practice in NiCd battery assembly for satellite applications.
Battery-to-cell weight ratio is an important figure-of-merit
for spacecraft applications. The battery-to-cell weight ratio
is significantly lower for DPV batteries in comparison to
standard IPV batteries. Generally, cells are arranged in two
arrays to form the battery assembly to provide a compact and
nearly square package for ease of integration into the space-
craft. To accommodate an odd number of cells, generally a
dummy cell is used which adds to the battery mass, but does
not contribute to energy storage.
The electrical design includes aspects and components
such as intercell connection, conductor losses, the battery
electrical interface, battery voltage, current and tempera-
ture monitoring, charge controllers, and battery electronics,
139
namely strain gauges, strain gauge amplifiers, heaters,
heater controllers, cell by-pass modules, cell voltage, cur-
rent and temperature monitoring depending on the specific
battery design. Strain gauge circuitry, in a full bridge
configuration, measures the microflex of the pressure vessel
produced by the internal pressure changes in the cell. The
strain gauge is calibrated after girth weld closure before
electrolyte activation by pressurising the cell with helium.
The strain gauge bridge has to be excited with a dc supply
(210 V) and the output has to be amplified and processed
to directly indicate the cell internal pressure and the cell
SOC. Three thermistors mounted at different locations in
the battery are used to check the uniformity of temperature
across the battery. A non-contact inductive type current
sensor is used to sense the battery current. All monitoring
information such as voltage, current, temperature and pres-
sure are sent to telemetry through a battery electrical inter-
face connector.
In order to achieve a long life, the NiH2 battery has to be
operated within a narrow band of temperature. Cell heaters
are used to help regulate cell temperature during orbital
operation. The cell reaction is endothermic during the bulk
of charging, and exothermic during overcharge and dis-
charge. The heat generated in the cell has to be conducted
to the spacecraft deck and subsequently radiated to space. In
DPV batteries, a thin aluminium thermal shim, which is
electrically insulating and thermally conducting, is inserted
between each pair of adjacent cells such that the flat side of
the pressure vessel makes contact with each cell through a
thermal shim. Each thermal shim has a flange which contacts
the battery base plate and acts as a heat sink. This arrange-
ment provides a large cross-sectional area for removal of
heat from the internal electrode stack. In DPV batteries, the
electrode stack is in direct contact with the flat pressure
vessel wall. By contrast, in IPV cells, the stack is not in
direct contact with the cylindrical pressure vessel and heat
can only be rejected by the electrode stack across a narrow
hydrogen gap between the stack and the pressure vessel wall.
DPV batteries provide a direct path for heat rejection by the
cell. DPV batteries use advanced fibre-based nickel electro-
des which have ca. 25% higher specific energy than standard
sintered-nickel aerospace electrodes. But, the fibre-based
nickel electrodes are to be qualified for space applications.
Testing and qualification of the fibre nickel electrodes are
important issues which are currently being addressed. DPV
cells provide energy density of 60 Wh kg1 and 73 Wh l1
in comparison to an IPV cell which provides only
53 Wh kg1 and 52 Wh l1. The high energy version of
DPV cells which use fibre nickel electrodes can provide
76 Wh kg1 and 89 Wh l1. The advanced design DPV cells
can provide up to 70 Wh kg1 at full battery level as against
42 Wh kg1 provided by the state-of-the-art IPV batteries
[36]. Developing a light weight pressure vessel capable of
containing hydrogen at around 1000 psi requires innovative
design, careful materials selection and manufacturing tech-
niques. A hydroforming process is considered to be most
140 A.K. Shukla et al. / Journal of Power Sources 100 (2001) 125148
suitable for this application. NiH2 batteries have certain
deficiencies such as low volumetric energy density, high
self-discharge rate, capacity loss on storage, high thermal
dissipation during high rate discharge, and safety hazards
due to high operating pressures. The low volumetric energy
density of the NiH2 batteries is overcome in the NiMH
battery system.
5. Nickelmetal hydride batteries
There is continuous effort to develop high energy density,
high power density and low-cost rechargeable batteries to
meet the ever increasing needs for spacecrafts, defence,
communication, electric vehicles, computers, camcorders,
cellular phones, power tools and other home appliances.
Until recently, mainly NiCd batteries were meeting these
requirements. NiMH batteries using hydrogen storage
alloys as the negative electrode material have been drawing
increasing attention due to their higher energy density both
in terms of weight and volume, improved high rate cap-
ability (the endothermic nature of the discharge reaction
allows high rate discharge with relatively less heat dissipa-
tion), and high tolerance to overdischarge. Furthermore,
sealed NiMH cells can be easily constructed because the
O2 and H2 gas evolved, respectively, during overcharge and
overdischarge are effectively consumed allowing prismatic
design with superior packaging and heat management cap-
abilities. These batteries are also free from dendrite forma-
tion and memory effect due to recrystallisation and are
devoid of toxic materials such as lead, cadmium, mercury
and asbestos although nickel is known to present health
hazards to humans.
Akin to the NiCd system, NiMH cells also employ
nickel positive plates with NiOOH as the active material and
an aqueous KOH electrolyte. The main difference is that the
active material in the negative plate is hydrogen absorbed in
a metal alloy. The metal alloys in which hydrogen is stored
fall into two categories: (a) the AB5-alloys based on mix-
tures of nickel and rare earth, and (b) the AB2-alloys based
on nickel commonly blended with titanium, vanadium and
zirconium. A typical composition of the AB5-alloy that has
been documented to be a promising electrode material is
Mm (Mm misch-metal: 25 wt.% La, 50 wt.% Ce, 7 wt.%
Pr, 18 wt.% Nd) Ni3.2Co1.0Mn0.6Al0.11Mo0.09 which has
CaCu5-type crystal structure. Among the AB2-type alloys,
Ti0.51Zr0.49V0.70Ni1.18Cr0.12 has been found to be an attrac-
tive electrode material which has 14 C-Laves crystal struc-
ture. In the beginning, AB5-type alloys were employed as
battery electrodes, but at present, AB2-type alloys are pre-
ferred electrode materials for NiMH batteries [38]. It is
found that while AB2-type alloys yield superior energy
storage densities, the AB5-alloys are able to hold hydrogen
better, thus, lowering the self-discharge rate of the battery.
Besides, AB5-alloys happen to be less expensive and easier
to use.
400 Ah kg1 and provide 80 Wh kg1 of
Historically, hydrides of binary intermetallic compounds
were first reported by Trzesciak et al. in 1956 [39]. In 1958,
Libowitz demonstrated reversible hydrogen absorption and
desorption in ZrNiH3 [39]. Soon other intermetallic hydrides
such as LaNi5 (AB5-alloy) which could absorb and desorb
large amounts of hydrogen were discovered [39]. Justi et al.
[40] were the first to investigate NiTi hydrides as reversible
hydrogen electrodes. During 1970s and 1980s, Daimler
Benz [41] carried out extensive studies on NiTi2 (AB2-alloy)
and NiTi (AB-alloy) intermetallic materials as hydrogen
storage materials for vehicular applications. Early studies on
Ni2Ti-based AB2 and AB alloys and LaNi5-based AB5-
alloys were found to have cycle lives which were too poor
to be useful for practical batteries [42]. Guegan et al. [43]
were first to recognise the correlation between the gaseous
pressure-composition isotherm and the electrochemical
properties of LaNi5-based alloys. Willems [44] suggested
that the long-term stability of LaNi5 electrodes can be
improved dramatically by partly replacing La and Ni by
other alloying elements, especially Co which is both expen-
sive and toxic. It was realised that partial substitution of Cr
and/or Ge for Ni in LaNi5-type alloys also improves the
performance of MH electrodes.
Most of the early studies on metal hydride alloys were
based on binary alloys which had the limitation of stability,
poor hydrogen storage capacity and life. Fig. 21 shows the
types of metal hydride formed between hydrogen and var-
ious other elements in the periodic table. The diverse proper-
ties required for a superior MH battery electrodes are
appropriate hydrogen binding energy, high hydrogen
absorption/storage capacity, fast electrode kinetics, good
H2O2 recombination rate, charge retention, chemical and
physical stability (oxidation/corrosion resistance), easy
manufacturability at a reasonable cost which can be
achieved through compositional and structural disorder in
multicomponent, mutiphase alloys introduced by specific
elemental modifiers [45,46]. According to Ovishinsky, a
typical disordered material contains five distinct composi-
tional phases and body-centred cubic, hexagonal and 14 C-
Laves crystal structures. Body-centred cubic structures can
store large quantities of H2, but lack electrocatalytic activity.
The hexagonal and 14 C-Laves phases effectively channel H2
for rapid electrochemical discharge. The basic multielement
multiphase alloys typically contain V, Ti, Zr, Ni, Cr, Co, Mn
and Fe. The alloying constituents, Ti, Zr and V primarily
provide H2 absoption, Co and Mn provide surface activity,
Ni provides catalytic activity for redox reaction and Cr and
Fe provide corrosion resistance [47,48].
At present, most commercial NiMH batteries either
employ AB5-type MmNi3.2Co1.0Mn0.6Al0.11Mo0.09 or
AB2-type Ti0.51Zr0.49V0.70Ni1.18Cr0.12 alloys. The commonly
used misch-metal alloys are capable of delivering a capacity
of only about 300 Ah kg1. While these alloys utilise
Ovishinskys concept of disorder, they do not compare to
commercial Ovonic transition metal alloys which exhibit
a capacity of
 A.K. Shukla et al. / Journal of Power Sources 100 (2001) 125148 141

Fig. 21. Periodic table showing types of metal-hydrides.

specific energy at cell level. This jump is only considered as a
first threshold to the projected capacity value of 700
1000 Ah kg1 in future phases. Mg-based alloys have been
projected as excellent materials for MH electrodes with
capacity values as high as 1000 Ah kg1 [49]. But, magne-
sium based alloys are prone to corrosion in alkaline environ-
ments. The major problems associated with these alloys are
the sluggish hydriding kinetics at room temperature and
oxidation of the material under ambient environmental con-
ditions [50].
Fig. 22 gives the operating principle of a sealed recharge-
able NiMH cell. The Ni(OH)2 at the positive electrode is
oxidised to NiOOH on charge and reduced back to Ni(OH)2
during discharge. During charge, at the MH negative elec-
trode, reduction of water produces atomic, adsorbed hydro-
gen which diffuses into the lattice of the intermetallic alloy

Fig. 22. Design principle of a sealed NiMH cell.

142 A.K. Shukla et al. / Journal of Power Sources 100 (2001) 125148
to form a metal hydride. A reverse reaction takes place
during discharge. Accordingly, the electrochemical reactions
occurring in a NiMH cell can be represented as follows:
discharge
NiOOH H2 O e @ NiOH2 OH
charge
0 4OH ! 2H2 O O2 4e
E 0:49 V versus SHE
and
discharge
MH OH 
@ M H2 O e 
charge
0 difference in storage capacities of series connected cells
E 0:83 V versus SHE
Accordingly, the overall cell reaction is
discharge
NiOOH MH @ NiOH2 M
charge
Ecell 1:32 V
The chargedischarge reactions in a NiMH battery
proceed via a homogeneous solid-state mechanism through
proton transfer between nickel hydroxide and hydrogen
storage alloy distinguishing it from other nickel-based bat-
teries where the anode reaction proceeds through a dissolu-
tionprecipitation mechanism. Hence, the source of many of
the performance deficiencies, such as (a) changes in crystal-
lography, (b) changes in mechanical integrity, (c) changes in
surface morphology of the electrode as a result of dissolution
and recrystallisation, and (d) reduced electrical conductivity
in the oxidised state, are eliminated in the NiMH system
permitting a more compact assembly, longer cycle-life and
the construction of a solid-state battery using a proton
conducting solid electrolyte [51,52].
As in the NiCd cell, the electrolyte is concentrated
aqueous KOH. As a consequence of reactions (41) and
(42), there is no net change in the electrolyte quantity or
concentration over the chargedischarge cycles. This is an
attractive feature of NiMH batteries over NiCd batteries
wherein water is generated during charge and consumed
during discharge. On the down side, NiMH batteries deliver
less power, have a faster self-discharge and are less tolerant
to overcharge like the NiCd batteries.
Since the nickel oxide electrode is thermodynamically
unstable in the cell environment, oxygen-evolution occurs at
this electrode as a parallel and competing reaction. The
parasitic reactions during charge are represented by
4OH ! 2H2 O O2 4e
and
Hadsorbed Hadsorbed ! H2
To ensure proper functioning of a sealed NiMH cell under a
variety of conditions, it is designed in such a way that the
capacity of the cell is limited by the positive electrode.
Accordingly, O2 evolution occurs at the positive electrode
during overcharge and this diffuses to the metal-hydride
electrode where it combines to form water. The negative to
positive capacity ratio varies between 1.5 and 2. Typically,
the discharge reserve is in the range of 20% of the positive
capacity.
Reactions during cell overcharge are
(46)
(41)
M H2 O e ! MH OH (47)
4MH O2 ! 4M 2H2 O (48)
Under deep-discharge conditions, due to the inevitable
(42)
in a NiMH battery, H2 evolution occurs at the positive
electrode which is oxidised to water at the MH electrode.
Thus, there are recombination mechanisms for both H2 and
O2 gases evolved during overdischarge and overcharge,
respectively, permitting sealed operation of the NiMH
(43) cells. Reactions during cell overdischarge are
H2 O e ! 12 H2 OH (49)
and
H2 2OH ! 2H2 O 2e (50)
Since the cell reaction causes no net change in the electrolyte
concentration or quantity, maintenance of electrolyte con-
centration results in good gas recombination, good high and
low temperature operations, and good resistance to cycle-
life limitations caused by corrosion and swelling.
NiMH cells are generally available in AA, sub-C and
C sizes. Prismatic cells up to 250 Ah are manufactured for
electric vehicle application by Ovonic Battery Company
(USA) and Gold Peak Industries (Hong Kong). The capacity
that can be obtained from a NiMH cell is about two times of
an equivalently sized NiCd cell. The NiMH cells can
operate from 20 to 458C. But, above 458C, the charge
efficiency falls steeply. The charge efficiency of NiMH cell
is better than NiCd cells for charge rates between C/10 and
C/20 at 208C. The voltage and temperature profiles during
charge at various rates are given in Fig. 23. The typical
voltage profile during charge at different temperatures is
given in Fig. 24. The internal pressure of the cell generally
does not exceed 50 psi for a C/10 charge at 208C. Typical
profile of internal pressure during charge at various rates
is shown in Fig. 25. The cell pressure increases both at
higher charge rates and at higher temperatures. Cylindrical
cells are provided with a safety vent operating at around
(44) 400 psi. Due to the endothermic nature of the discharge
process, the heat evolved during discharge is relatively less
than in NiCd cells at discharge rates less than C. Joule
heating masks the cooling due to endothermic desorption
(45)
of H2 during discharge. Cells can be discharged even at the
5C rate. The dependence of the discharge rate and the
discharge capacity is depicted in Fig. 26. The effect of
temperature on available capacity is given in Fig. 27. The
absorption of H2 during charge is an exothermic process. But
the temperature rise becomes noticeable only from the point
 A.K. Shukla et al. / Journal of Power Sources 100 (2001) 125148 143

Fig. 23. Typical voltage and temperature profiles for a NiMH cell during charge at various rates.

Fig. 24. Voltage profile for a NiMH cell during charge at different temperatures.

Fig. 25. Pressure profile for a NiMH cell during charge at various rates.
144 A.K. Shukla et al. / Journal of Power Sources 100 (2001) 125148

Fig. 26. Effect of discharge rate on capacity of a NiMH cell.

where O2 recombination begins to occur. During hydriding, of O2 according to following reactions:

the electronic conductivity decreases. If the overcharge is 2NiOOH H2 O ! 2NiOH2 12 O2 (51)
controlled then the heat generation in the cells is mainly due
to Joule heating. Cells can be charged at C rate. Monitoring O2 2H2 O 4e ! 4OH (52)
the inflection of charge voltage is considered to be the most  
MH OH ! M H2 O e (53)
appropriate method to prevent overcharge, and thus, to
improve the cycle-life of the cell. A cycle-life >1000 cycles 4MH O2 ! 4M 2H2 O (54)
at 100% depth-of-discharge (DOD) has been demonstrated. The highly facile O2 recombination reaction at the MH
Cycling at C/3 (charge for 65 min and C/1.6 discharge for alloy electrode can accelerate the decomposition of the
35 min) at 40% DOD with an overcharge factor of 1.02 at positive active material. Gaseous hydrogen, which is in
228C has been carried out for over 8000 cycles. Under equilibrium with the metal hydride alloy, can reduce the
similar conditions, a NiH2 cell requires 1.1 overcharge charged positive electrode as indicated below.
factor. NiMH cells have a higher rate of self-discharge in
relation to NiCd cells. 2NiOOH H2 ! 2NiOH2 (55)
Charged positive active material is thermodynamically It is noteworthy that H2 oxidation is inhibited by anodi-
unstable and can spontaneously decompose with evolution cally formed Ni(OH)2/NiOOH. But cathodically deposited

Fig. 27. Effect of temperature on available capacity of NiMH cells.

 A.K. Shukla et al. / Journal of Power Sources 100 (2001) 125148
Fig. 28. Comparison of charge-retention characteristics of NiMH cells.
Ni(OH)2 does not inhibit the reaction to the same degree.
Shuttle reactions due to the presence of impurities, such as
nitrate present in the electrodes and the electrolyte, con-
tribute to self-discharge to a significant extent in a fresh cell.
Oxidation of organic impurities that are extracted or leached
out from the separator at the positive electrode also con-
tribute to the self-discharge process. Metal ions leached out
from the MH alloy may have an adverse reaction at the
positive electrode. It is reported [33] that the main con-
tributing factor to the decomposition of the conventional
polyamide separator is the production of ammonia and
amines which participate in shuttle reactions similar to
NO3 ions in NiCd battery. Charge retention can be
drastically improved by using chemically stable separators
such as sulfonated polypropylene. Fig. 28 depicts the com-
parison of charge retention characteristics of NiMH cells
with different separator materials. Addition of Al and Zr
improves the charge retention in AB5-type alloys.
State-of-the-art NiMH cells have a specific energy of
95 Wh kg1 and a volumetric energy density of 330 Wh l1.
The specific power of the cells is 200 W kg1 and the power
density is 485 W l1. State-of-the-art metal hydride electro-
des are prepared from transition metal alloys with a non-
traditional structure design which deliver a capacity of 550
650 Ah kg1. Foam nickel with 9095% porosity is used as
the substrate for the positive electrode. The positive active
material is based on an a to g transformation as against the b
to b transformation in conventional NiCd cells.
A very common problem with hydrogen storage materials
is severe volume expansion during the chargedischarge
process giving rise to cracking and pulverisation of the alloy
making it amenable to oxidation. In addition, dissolution of
the alloy in the electrolyte contributes to capacity decay.
Present materials science strategies are concentrated on
combining different phases and microstructures to overcome
the short comings in the behaviour of the bulk metal hydride.
To increase rate capability, materials with high surface-area
are produced by powder metallurgy, mechanical alloying,
chemical or electrochemical etching. All the materials with
145
high surface-area invariably suffer from lower cycle-life due
to increased oxidation of the surface. The MH electrodes are
susceptible to wide spread cracking and irreversible oxida-
tion which affect their cycle-life, stability and rate capabil-
ity. Metallurgical processes such as encapsulation
(electroless plating of copper and nickel), doping with
palladium and cerium, rapid solidification, and macroalloy-
ing are found to have only limited success in reducing the
rate of degradation. Pure LaNi5 electrodes in contact with
KOH vapour undergo brittle fracture during hydriding
resulting in rapid decay of capacity with cycling. Cobalt
addition with aluminium or silicon has been found to sig-
nificantly improve the cycling behaviour of NiMH cells.
Laboratories around the world, in an effort to improve the
cycle-life and capacity of metal hydride cells, have
exhausted nearly all the elements in the periodic table in
preparing both AB2 and AB5 alloys.
The major problem with the metal hydride electrodes is
that the function of the alloying elements either acting alone
or in combination with other alloying elements cannot be
predicted unambiguously. Conventional AB5 and AB2
alloys based on LaNi5 and (Ti, Zr)Ni2 have relatively low
Coulombic capacity values between 300 and 450 Ah kg1
and hence, the present day research focuses on alloys such as
TiZrNi2 and Mg2Ni alloys as low cost, light weight and safer
alternatives. In order to increase the energy density of the
NiMH battery, it is mandatory to improve the performance
of metal-hydride electrodes. With a combination of modi-
fications in the alloy composition and new methods of
electrode preparation, discharge capacities between 630
and 780 Ah kg1 have been achieved at a discharge current
density of 50 A kg1 for Mg-based alloy (Mg1.9Al0.1Ni0.8-
Co0.1Mn0.1) electrodes [53]. An amorphous structure
appears to be central in achieving high discharge capacities.
These encouraging results indicate that the kinetics of
hydriding/de-hydriding reactions of Mg-based alloy elec-
trodes can be greatly improved by ball-milling and chemical
coating. Efforts are being directed towards maintaining
particle-to-particle electrical contact by the use of polymer
binders, compaction of porous nickel foam, surface plating
as well as doping and compaction with conductive powders.
The performance of the NiMH batteries has seen contin-
uous improvements over the years since 1991 through a
combination of approaches such as high density negative
electrodes, thinner separators, upgraded positive electrodes
and improved packaging efficiencies.
6. Nickelzinc batteries
In the NiZn battery, zinc electrodes operate on the
following dissolutionprecipitation reactions.
discharge
Zn 4OH @ ZnOH4 2 2e
charge
0
E 1:20 V versus SHE (56)
146 A.K. Shukla et al. / Journal of Power Sources 100 (2001) 125148
The following precipitation reaction occurs concomi-
tantly:
discharge
ZnOH4 2 @ ZnO 2OH H2 O (57)
charge
ZnO produced during reaction (57) has the tendency to
dissolve in aqueous KOH. As described earlier, the
chargedischarge reactions occurring at the nickel positive
electrode in the battery are
discharge
2NiOOH 2H2 O 2e @ 2NiOH2 2OH
charge
0
E 0:49 V versus SHE (58)
Accordingly, the overall cell discharge and charge reactions
are expressed as
discharge
Zn 2NiOOH H2 O @ ZnO 2NiOH2
charge
Ecell 1:75 V (59)
The electrolyte is usually 2035 wt.% aqueous KOH with
1 wt.% LiOH which is saturated with ZnO. The LiOH
addition enhances the charge acceptance of NiOOH elec-
trode. Similarly, addition of NaOH to KOH has been found
to extend the service life of NiZn batteries while operating
them at temperatures >508C. The NiZn battery is a promis-
ing alkaline storage battery and exhibits attractive perfor-
mance with energy density values between 55 and
85 Wh kg1, power density values between 140 and
200 W kg1, and a self-discharge rate less than 0.8% per
day. Besides, electrode materials used in the NiZn batteries
are abundant, and cost-effective. The batteries are produced
in various configurations, namely vented static-electrolyte,
sealed static-electrolyte, vibrating electrolyte and flowing
electrolyte configurations [5456]. Seminal features for
these designs are briefly highlighted below.
Vented static-electrolyte nickel-zinc cells are designed to
be positive-limited. While nickel positive electrodes are of
the conventional sintered type formed either by an electro-
chemical or chemical precipitation process, the porous zinc
negative electrode comprises a polymer-bonded paste of
ZnO bonded to a current collecting mesh or screen. Calcium
is a beneficial additive to the zinc electrode. When Ca(OH)2
3008C, there are no
is added to ZnO in alkaline electrolyte, an insoluble calcium
zincate compound is formed thereby trapping the soluble
Zn(OH)42 species. It has been found that both the active-
mass ratio of the negative and positive plates and the zinc to
electrolyte mass ratio in the NiZn batteries critically affect
the service life of the batteries. Various cell designs employ
microporous separators to avoid the growth of zinc dendrites
and wicking materials are used to help wetting the electro-
des. These cells are vented to the atmosphere to allow the
release of oxygen gas evolved during the charging process.
The cells are held under compression to avoid the occur-
rence of any deformity during their service life. Sealed
static-electrolyte NiZn cells find applications that require
low maintenance and safe operation. These batteries are akin
to vented static electrolyte batteries in various design fea-
tures, but the oxygen evolved at the nickel positive electro-
des during the charging process is efficiently transferred to
recombine at zinc electrode. In the vibrating-electrode Ni
Zn cells, a cam arrangement is used to vibrate the planar zinc
electrode which agitates the electrolyte and results in uni-
form zincate-ion concentration which effectively eliminates
the zinc active material redistribution problem. But owing to
the complex mechanical components, such NiZn batteries
are no longer under production. In the flowing-electrolyte
NiZn batteries, zinc-coated polymer beads are circulated to
the negative electrode compartment. These cells also are no
longer under production.
After years of development and several patent awards,
NiZn batteries have achieved commercial viability. Pre-
sent-day NiZn batteries are in performance comparable
with NiCd and NiMH systems. The low material and
manufacturing costs might make NiZn batteries competi-
tive even with the lead-acid batteries. Indeed, NiZn battery
technology has been licensed to several commercial entities
for a variety of applications. A small scale manufacturing
facility in the United States is currently producing commer-
cial grade NiZn batteries and a full-scale manufacturing
joint-venture is coming online in China in the near-term.
7. Sodiumnickel chloride (zebra) batteries
In addition to the batteries described in the earlier sec-
tions, there is a high-temperature nickel-based battery in
which the problem of dendritic-sodium growth in sodium
sulfur batteries has been cleverly circumvented with the use
of sodium tetrachloro aluminate (NaAlCl4) in conjunction
with Nab-alumina ceramic electrolyte. This battery was
invented in 1985 by Coetzer in Pretoria (South Africa).
Zebra stands for ZEolite applied to Battery Research Africa
[57,58]. The battery operates at about 3008C and the charge
discharge reactions during the cell operation are as follows:
discharge
2Na NiCl2 @ 2NaCl Ni Ecell 2:58 V (60)
charge
Since zebra batteries operate at
detrimental effects resulting from their use at extremely
cold or hot ambient temperatures. For conventional battery
systems, extreme temperatures require more elaborate ther-
mal management or result in reduced battery performance.
Besides, because of their high-temperature operation, zebra
batteries allow for the use of latent heat for fast cabin heating
or window defrosting. But the thermal management needs
for the high-temperature zebra batteries are not quite ideal
for electric vehicle-drive-systems. When not in use, zebra
batteries typically require being plugged into a wall plug, or
tethered, in order to be ready for use when needed. If shut
down, a reheating process must be initiated that requires
about one to 2 days to restore the battery pack to the desired
 A.K. Shukla et al. / Journal of Power Sources 100 (2001) 125148
temperature, and fully charging the batteries. This reheating
time can, however, vary depending on the SOC of the
batteries at the time of their shut down, battery-pack tem-
perature, and power availed for reheating. If shut down of the
battery pack is desired, three to 4 days are usually required
for a fully-charged battery pack to lose its heat significantly.
This battery is described in more details in the paper by
Sudworth elsewhere in this volume.
8. Conclusions
Among the various nickel-based batteries reviewed
above, NiMH batteries seem to have widespread commer-
cial viability and significant opportunity for improvement.
NiMH batteries appear to be the technology of choice for
the emerging electric vehicles, hybrid electric vehicles and
fuel cell electric vehicles. Important advances in positive
and negative electrode materials have allowed, for the first
time, prototype NiMH batteries of over 100 Wh kg1
specific energy. At the same time, specific power has been
increased from 150 to over 1000 W kg1, with further
advances observed in the laboratory. Today, NiMH bat-
teries occupy a unique position within the battery industry.
NiMH batteries are rapidly growing and gaining an excel-
lent reception in the market. Next generation improvements
in NiMH batteries are already being implemented with still
further improvements targeted.
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